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A Study on IIIA Group Metals (B or Ga or Tl) Doped Mo2C-HZSM-5 Catalysts for Methane Dehydroaromatization

Chemical and Materials Engineering Department, Faculty of Engineering, King Abdulaziz University, P.O. Box 80204, Jeddah, 21589, Saudi Arabia

Received: 26 Aug 2025; Revised: 14 Sep 2025; Accepted: 15 Sep 2025; Available online: 19 Sep 2025; Published: 26 Dec 2025.
Editor(s): Istadi Istadi
Corrigendum to this article (DOI: https://doi.org/10.9767/bcrec.20477) has been published in DOI: https://doi.org/10.9767/bcrec.20643
Open Access Copyright (c) 2025 by Authors, Published by BCREC Publishing Group
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Abstract

Methane dehydroaromatization (MDA) is a promising route for direct conversion of methane into value-added aromatics such as benzene, toluene and naphthalene. This study investigates the effect of IIIA group metals like boron (B), gallium (Ga), and thallium (Tl) doped into Mo₂C/HZSM-5 catalysts tested for MDA at 700 oC and 1800 mL.gcat-1.h-1. The influence of promoters on catalyst acidity and coke formation was investigated through various analytical techniques including NH₃-TPD and TPO. Among the samples, Ga-Mo₂C/HZSM-5 demonstrated greater benzene selectivity and consistent stability due to abundant Mo2C and low temperature coke formations. Whereas, B- or Tl-Mo₂C/HZSM-5 suffered from high temperature coke formations related to their greater acidity and greater extent of surface molybdenum oxidized species. Copyright © 2025 by Authors, Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Keywords: MDA; Benzene; naphthalene; Mo2C; HZSM-5
Funding: King Abdulaziz University under contract DSR 355-135-1443

Article Metrics:

  1. Zhu, P., Bian, W., Liu, B., Hao, D., Lucun, W., Xiaozhou, H., Stephanie, L.S., Feng, L., Chuancheng, D., Dong, D., Pei, D., Hanping, D (2024). Direct conversion of methane to aromatics and hydrogen via a heterogeneous trimetallic synergistic catalyst. Nature Communications. 15, 3280. DOI: 10.1038/s41467-024-47595-9
  2. Hu, J., Yang, C., Liu, B., Zhao, X., Wang, Y., Wang, X., Liu, J., Guan, J. (2023). Improving the methane aromatization activity and anti-carbon deposition on MCM-22 through nano α-MoO₃ modification. New Journal of Chemistry. 47, 2949–2956. DOI: 10.1039/D2NJ05415A
  3. Spivey, J.J., Hutchings, G. (2014). Catalytic aromatization of methane. Chemical Society Reviews. 43, 792–803. DOI: 10.1039/C3CS60259A
  4. Emmanuel, A., Devi, P.R., Mathew, T.V. (2024). Reserves and natural gas sources of methane emissions: Greenhouse gas. In Greenhouse Gases Emissions and Climate Change, 53–70. DOI: 10.1016/B978-0-443-19231-9.00017-X
  5. Liu, Y., Ćoza, M., Drozhzhin, V., van den Bosch, Y., Meng, L., van de Poll, R., Hensen, E.J.M., Kosinov, N. (2023). Transition-metal catalysts for methane dehydroaromatization (Mo, Re, Fe): Activity, stability, active sites, and carbon deposits. ACS Catalysis. 13(1), 1–10. DOI: 10.1021/acscatal.2c04962
  6. Kosinov, N., Coumans, F.J.A.G., Uslamin, E.A., Wijpkema, A.S.G., Mezari, B., Hensen, E.J.M. (2017). Methane dehydroaromatization by Mo/HZSM-5: Mono- or bifunctional catalysis. ACS Catalysis. 7(1), 520–529. DOI: 10.1021/acscatal.6b02497
  7. Qi, S., Yang, B. (2004). Methane aromatization using Mo-based catalysts prepared by microwave heating. Catalysis Today. 98, 639–645. DOI: 10.1016/j.cattod.2004.09.049
  8. López-Martín, A., Sini, M.F., Cutrufello, M.G., Caballero, A., Colón, G. (2022). Characterization of Re-Mo/ZSM-5 catalysts: How Re improves the performance of Mo in the methane dehydroaromatization reaction. Applied Catalysis B: Environmental. 304, 120960. DOI: 10.1016/j.apcatb.2021.120960
  9. Wang, L., Ohnishi, R., Ichikawa, M. (2000). Selective dehydroaromatization of methane toward benzene on Re/HZSM-5 catalysts and effects of CO/CO₂ addition. Journal of Catalysis. 190(2), 276–283. DOI: 10.1006/jcat.1999.2748
  10. Tshabalala, T.E., Coville, N.J., Anderson, J.A., Michael, S.S. (2021). Dehydroaromatization of methane over noble metal loaded Mo/H-ZSM-5 zeolite catalysts. Applied Petrochemical Research. 11, 235–248. DOI: 10.1007/s13203-021-00274-y
  11. Pasupulety, N., Al-Zahrani, A.A., Daous, M.A., Driss, H., Petrov, L.A. (2021). Methane aromatization study on M-Mo₂C/HZSM-5 (M = Ce or Pd or Nb) nanomaterials. Journal of Materials Research and Technology. 14, 363–373. DOI: 10.1016/j.jmrt.2021.06.058
  12. Denardin, F., Perez-Lopez, O.W. (2019). Tuning the acidity and reducibility of Fe/ZSM-5 catalysts for methane dehydroaromatization. Fuel. 236, 1293–1300. DOI: 10.1016/j.fuel.2018.09.128
  13. Gan, Y., Xu, Y., Zhang, P., Wang, W., Liu, W., Li, R., Xu, X., Wu, L., Tang, Y., Tan, L. (2024). Boron doped Mo/HMCM-22 catalyst for improving coke resistance in methane dehydroaromatization. Chemical Engineering Science. 299, 120485. DOI: 10.1016/j.ces.2024.120485
  14. Dutta, K., Li, L., Gupta, P., Pacheco Gutierrez, D., Kopyscinski, J. (2018). Direct non-oxidative methane aromatization over gallium nitride catalyst in a continuous flow reactor. Catalysis Communications. 106, 16–19. DOI: 10.1016/j.catcom.2017.12.005
  15. Carneiro, V.M.T., Longo, L.S., Silva, L.F. (2015). Sustainable catalysis using non-endangered metals. In North, M. (Ed.), Sustainable Catalysis: With Non-endangered Metals, Part 2, 212–230. The Royal Society of Chemistry: Cambridge
  16. Rahele, M., Lars-Åke, N., Joseph, H., Jun, L., Michel, W.B., Johanna, R. (2015). Synthesis of two-dimensional molybdenum carbide, Mo₂C, from the gallium based atomic laminate Mo₂Ga₂C. Scripta Materialia. 108, 147–150. DOI: 10.1016/j.scriptamat.2015.07.003
  17. Matthew, Y., Peng, H., Jack, J., Shijun, M., Aiguo, W., Shiyu, K., Richard, G., Lijia, L,, Hua, S. (2018). Co-aromatization of methane with olefins: The role of inner pore and external surface catalytic sites. Applied Catalysis B: Environmental. 234, 1–10. DOI: 10.1016/j.apcatb.2018.04.034
  18. Busca, G. (2017). Acidity and basicity of zeolites: A fundamental approach. Microporous and Mesoporous Materials. 254, 3–16. DOI: 10.1016/j.micromeso.2017.04.007
  19. Medak, G., Puškarić, A., Bronić, J. (2023). The Influence of Inserted Metal Ions on Acid Strength of OH Groups in Faujasite. Crystals. 13(2), 332. DOI: 10.3390/cryst13020332
  20. Chen, J., Liang, T., Li, J., Wang, S., Qin, Z., Wang, P., Huang, L., Fan, W., Wang, J. (2016). Regulation of Framework Aluminum Siting and Acid Distribution in H-MCM-22 by Boron Incorporation and Its Effect on the Catalytic Performance in Methanol to Hydrocarbons. ACS Catalysis. 6(4), 2299–2313. DOI: 10.1021/acscatal.5b02862
  21. Mudi, X., Enhui, X., Xiuzhi, G., Yongrui, W., Ying, O., Guangtong, X., Yibin, L., Xingtian, S. (2019). Ga Substitution during Modification of ZSM-5 and Its Influences on Catalytic Aromatization Performance. Ind. Eng. Chem. Res. 58 (17), 6970–6981. DOI: 10.1021/acs.iecr.9b00295
  22. Khademi, A., Azimirad, R., Zavarian, A., Moshfegh, A. (2009). Growth and Field Emission Study of Molybdenum Oxide Nanostars. Journal of Physical Chemistry C. 113(45), 19298–19304. DOI: 10.1021/jp9056237
  23. Hu, H., Wachs, I.E., Bare, S.R. (1995). Surface Structures of Supported Molybdenum Oxide Catalysts: Characterization by Raman and Mo L3-Edge XANES. The Journal of Physical Chemistry. 99(27), 10897–10910. DOI: 10.1021/j100027a030
  24. Briggs, D., Seah, M.P. (1990). Practical Surface Analysis, 2nd ed. Wiley: Chichester, UK
  25. Pasupulety, N., Al-Zahrani, A.A., Daous, M.A., Driss, H., Petrov, L.A. (2020). Studies on molybdenum carbide supported HZSM-5 (Si/Al = 23, 30, 50 and 80) catalysts for aromatization of methane. Arabian Journal of Chemistry. 13(5), 5199–5207. DOI: 10.1016/j.arabjc.2020.02.016
  26. Li, H., Zhang, W., Liu, Y. (2020). HZSM-5 zeolite supported boron-doped TiO2 for photocatalytic degradation of ofloxacin. Journal of Materials Research and Technology. 9(3), 2557–2567. DOI: 10.1016/j.jmrt.2019.12.086
  27. Uslamin, E.A., Luna-Murillo, B., Kosinov, N., Bruijnincx, P.C.A., Pidko, E.A., Weckhuysen, B.M., Hensen, E.J.M. (2019). Gallium-promoted HZSM-5 zeolites as efficient catalysts for the aromatization of biomass-derived furans. Chemical Engineering Science, 198, 305–316. DOI: 10.1016/j.ces.2018.09.023
  28. Xin, M., Xing, E., Gao, X., Wang, Y., Ouyang, Y., Xu, G., Luo, Y., Shu, X. (2019). Ga substitution during modification of ZSM-5 and its influences on catalytic aromatization performance. Industrial & Engineering Chemistry Research, 58(17), 6970–6981. DOI: 10.1021/acs.iecr.9b00295
  29. Gaur, G.K., Srivastava, S. (2012). Characterization, XPS and toxicological study of organothallium (III) compounds with Schiff base ligands. Crystal Structure Theory and Applications, 1(3), 97–99. DOI: 10.4236/csta.2012.13018
  30. Leclair, P., Kohlhepp, J.T., Smits, A.A., Swagten, H.J.M. (2000). Optical and in situ characterization of plasma oxidized Al for magnetic tunnel junctions. Journal of Applied Physics, 87(9), 6070–6072. DOI: 10.1063/1.372615
  31. Huang, X., Wang, L., Gao, L., Jiao, X., Guo, X. (2025). Boron assists molybdenum to be confining single atoms for methane dehydroaromatization. Fuel, 384, 134040. DOI: 10.1016/j.fuel.2024.134040
  32. Guisnet, M., Gilson, J.-P. (2002). Zeolites for Cleaner Technologies. Imperial College Press: London, UK
  33. Song, C., Gim, M. Y., Lim, Y. H., & Kim, D. H. (2019). Enhanced yield of benzene, toluene, and xylene from the co‑aromatization of methane and propane over gallium supported on mesoporous ZSM‑5 and ZSM‑11. Fuel, 251, 404–412. DOI: 10.1016/j.fuel.2019.04.079
  34. Sonit, B., Ali, H. M., Tuhin, S.K., Pant, K.K. (2020). Boric acid treated HZSM-5 for improved catalyst activity in non-oxidative methane dehydroaromatization. Catal. Sci. Technol. 10, 3857-3867. DOI: 10.1039/D0CY00286K
  35. Huang, M., Li, J., Liu, Q., Zhang, M., Liu, Z., Gao, B. (2023). Enhanced catalytic performance of the hollow Mo/HZSM‑5 nanocrystal for methane dehydroaromatization. Fuel, 334 (Part 2), 126765. DOI: 10.1016/j.fuel.2022.126765
  36. Liu, S., Wang, L., Ohnishi, R., Ichikawa, M. (1999). Bifunctional catalysis of Mo/HZSM‑5 in the dehydroaromatization of methane to benzene and naphthalene: XAFS/TG/DTA/MASS/FTIR characterization and supporting effects. Journal of Catalysis, 181, 175–188. DOI: 10.1006/jcat.1998.2310
  37. Lee, B.J., Hur, Y.G., Kim, D.H., Lee, S.H., Lee, K.‑Y. (2019). Non‑oxidative aromatization and ethylene formation over Ga/HZSM‑5 catalysts using a mixed feed of methane and ethane. Fuel, 253, 449–459. DOI: 10.1016/j.fuel.2019.05.014
  38. Mishra, D., Modak, A., Pant, K.K., Zhao, G.X.S. (2022). Improved benzene selectivity for methane dehydroaromatization via modifying the zeolitic pores by dual‑templating approach. SSRN Electronic Journal. DOI: 10.2139/ssrn.4121584
  39. Ertl, G., Knözinger, H., Schüth, F., Weitkamp, J. (2008). Handbook of Heterogeneous Catalysis. Wiley-VCH: Weinheim, Germany
  40. Deepti, M., Arindam, M., Pant, K.K., Xiu, S. Z. (2022). Improved benzene selectivity for methane dehydroaromatization via modifying the zeolitic pores by dual-templating approach. Microporous and Mesoporous Materials. 344, 112172. DOI: 10.1016/j.micromeso.2022.112172

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